Photographic silver halide emulsions



' 5 color picture by photography and clnematogexample, l-amino- 4' -cyclohexyldiphenyl-ether, 5

m ore containing difierent coupling components one matic ring or in the hydrogenated heterocyclic 4515 proved iilm for color photography having super= each other on one or Tooth sides of a support.

Patente d Jan. 9, 1940 I I v I I I I ruse-no PnoToGnArnro SILVER n EMULSIONS Ali'red Friihlloh and Wilhelm Schneider, Dessau,

Germany, assignors, by mesue assignments, to Azi'a Ansco Corporation, Blnghamton, N. Y., a corporation of Delaware No Drawing. Application November 18, 1937, Serial No. 175,285. lln Germany. December 18,

ll-(llalms. (Cl. 956) This invention relates to color photography and molecule of a dyestufl intermediate product sub-' more particularly to a new and improved photostituents which areradicals of hyclro-eromatic or graphic material for color forming development. mixed aromatic-hydroaromatic or hydrogenated In the manufacture of color transparencies and heterocyclic compounds. Such compounds are for raphy it has been proposed to use silver halide 2:4-.-diamino-4-cyclohexyl diphenyl-ether, l-cy emulsions containing dyestufi components. The clohexyl-4-aminobenzene-5-sulfonic acid, paramode oi producing the color picture dlfifers with amino-cyclohexylhenzene, aminotetraline, arninothe nature of the dyestuff components. InU. S. decallne, amino-dicyclohexyl, i-cyclohexyl ben- Patents Nos. 1,102,028 and 1,055,155 dyestufi cornzoic acid, -cyclohexyl benzaldehyde, o-amino ponents are used which yield dyestu'fl pictures tetrehydroquinoline. The dyestufi component with certain developers by color forming developmay be united to a body of this kind with the ment. For producing multi color pictures it has aid of a reactive atom or atom group which may been proposed to cost severel liohtsensitive lay-= be present in the hydrogenated ring, in the aroupon the other and in order to avoid diil'usion of ring. The several rings may also contain one the coupling components the light-sensitive lay or more of the substituents disclosed in the U. S. ers have been isolated from each other by interpatents and U. S. patent applications referred m mediate layers. it has been shown, however. that to above. These substituents have already e. ten= 1 this precaution does not prevent the clifiusion to dency to make the molecule of the dyestuil com= the extent required by practice. The problem ponent fast to clifiusion. Dyestuir components lnhas been solved by using dyestufi components to which the radical of the hyclrouromatic or hy-- which are fast to difiuslon and for the first time drog'enized heterocyclic compound may be intro :2. process hes been attained by which a multi duceol are, for example, or and c=hydrorynaphlayer film yields a color picture by e. simple cle-= thoic acids, 2.3-hydroxyonthrecene carhonylic $5 velopment process (see U. 3. Patents 2379,2323, acid, salicylic acid, hydronyliuorene cerbonylic 2,178,612 and 2,179,244 and U. S. patent acid. 2.3-=hydrouyco.rbezole onrhonylic sold, o tions, Ser. No. eerie filed August 6, F No. naphthol aldehyde, l umino phenyl-3methyl-5 159,518 filed August 1'2, 1937, her. his. l 0,1399 filed pyrazolone, aromatic amines, eniinone ohthols, w September it, 1937). A further possibility of amlnonaphthol carhorrylic acids, eminonaphthol rendering dyestufi components fast to difiusion sulfonlc acids, ominophenols, eminohenzoyl ecetlc consists in introducing into their molecule at acid ester arylldes, un'ilnonaphthoyl ucetic ecid sterol radical ortollnlr up the dyestufi component ester erylldes, acyl acetic sold ester eminoaryl molecules in s chain like manner. ides or the like. The component may also be 535 This invention has for an object to provide it built up from the said compounds which hinder new range of dyestuid components with improved diffusion, for example, the pyrezolone from l= properties. cycloheryl phenyl hydrazine and ethyl eceto A iurther object is the provision or silver halide acetate. emulsions having incorporated the new. dyesturi The dyestuff components used in the invention w components fast to ditlusion. may be added to the emulsion at any point of its A further object is the provision of silver halide production. The silver halide emulsions thus on emulsions having, incorporated the new dyestuff teined are especially suitable for the purpose of, components fast to ciifiusion in a dissolved form. color photographyand may be made into layers A further object is the provision of an im=- in known mannen'loelne applied superimposed on posed silver halide emulsion'leyers et least one They may be sensitized ior various regions of the of said layers sum: a dyestufi? component spectrum. Emulsions may be applied, however, made fast to diffusion by the introduction into in another manner, for example the several sensi= its molecule of a radical according to this inventired emulsions having the different. dyestufi tion. formers may be brought on to the support in the so Further objects will be seen from the detailed form of small particles. The emulsion layers specification followinghereaiter. used in the invention may be combined with other The present invention is based on a process in layers in which-the color picture is producedby which especially useful dyestuil formers fast to a diflerent process, for example by mordantdyediffusion 'are obtained by introducing intmtho in: or by toning. Furthermore, the emulsion lay- 88 2,179,244 and U. S. applications ers of the invention may be combined with other layers which contain other dyestufl formers fast to difiusion, as described in the U. S. patent applications cited hereunder.

The colored pictures may be produced in various manners, for example by the processes of U. S. Patents 2,179,228, 2,179,238, 2,178,612 and Serial No. 94,340 filed August 5, 1936, Ser. No. 141,093 filed May 6, 1937, Ser. No. 159,518 filed August 17, 1937 and Ser. No. 164,499 filed September 18, 1937. Or the components located in multi-layer film may be converted into azo-dyes following development and fixing by such as a carbonic acid benzidine disul'fonic acid. There is thus produced in each emulsion layer together with a silver picture a dyestufi in which no structure can be perceived by magnification. The film is then treated with a silver bleaching out bath, i. e. that described in British Patent 401,340 to produce the dye image.

The exposed emulsion layers may be developed by a simple color forming development or by a reversal development as described in U. S. Patent 2,179,234. The pictures may also be produced in multi-layer material, each layer containing one solution of tetrazotized of said dyestufi components by exposing the material, developing to black and white in for instance Amidol, dissolving silver from the negative so produced by bleaching in for example a chromic acid bath, forming images in the remaining silver halide, developing in a developer such as is used above, forming silver halide images by treatment in a bleaching bath 1. e. again of chromic acid, forming latent images, transiorxm' ing the images into silver and color images in a developer capable of forming dyestuffs with said dyestufi component, removing the developed silver and fixing in thiosulfate. In the production of color pictures the silver is generally completely removed. In the production of black-and-white pictures with the aid of the silver halide emulsion layers produced in accordance with this invention the silver may be removed or may remain in the layer. The following examples illustrate the invention:

1. Ethylbenzoylacetate is condensed with 4- amino-phenyl-4'-cyclohexylbenzene:

when this body is added to a silver halide emulcondensed with d-cyclohe'xyl bensoic ch1o-" treatment with a diazo compound addition A compound of the following formula results:

ride. A compound of the following formula results: H:C---(l'J-CH3 H:CC-CH:

NELQ 0 Ha I l A silver halide emulsion which has received an of this body and has been worked up in manner similar to that described in Example 1' produces in the first case a red and in the second case a yellow dyestufi picture.

v 3. 2.3-hydroxynaphthoic acid chloride is con- 90 densed with 4.4-dicyclohexylaniline:

-OH+CtHn-CHn-CeH4-NHH as A compound of the following formula resultsr NEOO The silver halide emulsion to which this body has been added yields when exposed and developed by the anti-diazotate process a red dyestui! picture.

4. 2.3-hydroxycarba'zole carboxylic acid and,

ride is condensed with 6-mino-N-ethyl-tetra-'- line:

.genated said group 5. l-amino--naphthol is condensed with perhydrodiphenyl carboxylic acid:

n 'A' compound of the following formula results:

III:

H When this body is added to a photographic silver halide emulsion which is then exposed to light and developed by color forming development there is obtained a blue dyestufr picture. When the development is by the anti-diazotate process there is obtained according to the diazo-compound used a red to violet dyestufi picture.

6. a-hydroxynaphthoic acid chloride is condensed with perhydro-4-aminodiphenyl:

A compound of the following formula results:

H r m-co n I n.

H H, H\ \H When this body is added to a silver halide emulsion it is then exposed to' light and after development treated with a solution of tetrazotized 3.3- dicarboxylic acid and then by the known silver bleaching out process there is obtained a blue-red by a direct nuclear carboxylic acid radical the hydroxyl group of which is substituted by an amine radical having at least two organic rings, one of which at least is hydrogenated, said amine radical-being capable of rendering said dyestufl component fast to, diflusion in said silver halide emulsion.

3. A silver halide emulsion for color photography containing a dyestufi component for color forming development having attached thereto an amino group one hydrogen atom of which is substituted by the radical of an :'organic carboxylic acid having at least two organic rings one of which at least is hydrogenated said carboxylic acid radical being capabl of rendering said dyestufi component fast to difiusion in said silver halide emulsion.

4; The silver halide emulsion defined in claim 1 wherein said two rings are selected from the class consisting of fused rings and rings linked together carbon to nuclear carbon linkage.

5. A silver halide gelatine emulsion for color photography containing a dyestufi component for -color forming development having attached thereto by an acid amide linkage a group having at least 2,6-membered isocyclic rings linked together by a direct nuclear carbon to nuclear carbon linkage, at least one of said rings being hydrogenated, said group being capable of rendering said dyestufi component fast to diffusion in said silver halide emulsion.

6. The silver halide emulsion defined in claim 5, wherein said hydrogenated ring is cyclohexyl.

- 7. A silver halide gelatine emulsion for color photography containing a dyestufl component for color forming development having attached thereto by an acid amide linkage a group having 2 fused rings, one of which is heterocyclic and one of which is hydrogenated, said group being capable of rendering said dyestuff component fast to diifusion in said silver halide emulsion.

,8. The silver halide emulsion defined in claim 7,

wherein said group having 2 hydrogenated quinoline.

9. A silver halide gelatlne emulsion for color photography containing a dyestufi component for color forming development fast to diffusion in said silver halide emulsion, said dyestuif component being the condensation product of ethylbenzoyl acetate with 4-amino-phenyl-4'-cyclohexylbenzene. r

10. A silver halide gelatineemulsion for color photography containing a dyestufl component for fused rings is a color forming development which is fast to diflusion in said silver halide emulsion, said dyestufi component being a condensation product of 1-aminophenyl-3-methyl-5-pyrazolone with 4- cyclohexyl-benzoic acid chloride.

11. A silver halide gelatineemulsion for color photography containing a dyestufi component for color forming development which is fast to diffusion in said silver halide emulsion, said dyestufi component being the condensation product of 2.3-hydroxy carbazole carboxylic acid chloride with 6-N-ethyl-aminotetrahydroquinoline.

ALFRED mommcn. 

